CN1291998A - 用双-和多-2-噁唑烷酮交联水凝胶的方法 - Google Patents
用双-和多-2-噁唑烷酮交联水凝胶的方法 Download PDFInfo
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- CN1291998A CN1291998A CN99803378A CN99803378A CN1291998A CN 1291998 A CN1291998 A CN 1291998A CN 99803378 A CN99803378 A CN 99803378A CN 99803378 A CN99803378 A CN 99803378A CN 1291998 A CN1291998 A CN 1291998A
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- acid
- water
- oxazolidone
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Abstract
本发明包括吸水性聚合物的表面后交联的方法,其中聚合物用表面后交联溶液处理且在处理过程中或处理之后通过升温进行后交联和随后加以干燥,其中交联剂包括溶于惰性溶剂中的、包含以下通式的结构单元的双-2-噁唑烷酮或多-2-噁唑烷酮其中R1是支化或未支化C1-C18-亚烷基,支化或未支化C2-C18-亚链烯基,C5-C8-亚环烷基,亚苯基,亚萘基,亚蒽基,烃取代的亚苯基、亚萘基或亚蒽基或另外的取代或未被取代的C6-C18-亚芳基,R2是支化或未支化C1-C18-亚烷基和n是1—50的整数,另外,该交联剂可还含有双-2-噁唑烷酮和多-2-噁唑烷酮的混合物。
Description
本发明涉及利用双和多-2-噁唑烷酮的共聚合使吸水性水凝胶发生凝胶或表面后交联的方法。
亲水性可高度溶胀的水凝胶尤其是由(共)聚合的亲水性单体组成的聚合物,或是一种或多种亲水性单体在合适接枝基质物上的接枝(共)聚合物,交联纤维素醚或交联淀粉醚,交联羧甲基纤维素,部分交联聚亚烷基氧化物,或可在含水液体中溶胀的天然产物如瓜耳树胶衍生物。此类水凝胶可在尿布、棉塞、卫生巾和其它卫生制品的生产中用作吸收水溶液的产品,以及用作商品蔬菜栽培中的水份保持品。
为了改进工作性能如尿布再润湿和AUL,亲水性的可高度溶胀的水凝胶一般进行表面或凝胶相后交联。这一后交联对于本技术领域中的那些熟练人员来说是已知的并优选在含水的凝胶相中进行或以研碎的和过筛的聚合物颗粒的表面后交联方式进行。
适合此目的交联剂是包括至少两个能够与亲水聚合物的羧基形成共价键的基团的化合物。适宜交联剂的实例是二缩水甘油基或多缩水甘油基化合物如膦酸二缩水甘油基酯,烷氧基甲硅烷基化合物,聚氮丙啶,多胺或聚酰胺基胺,并且这些化合物还可以以相互之间的混合物使用(参见例如EP-A-0083022,EP-A-0543303或EP-A-0530438)。适合作为交联剂的聚酰胺基胺特别描述在EP-A-0349935。
这些交联剂的主要缺点是它们的高反应活性。虽然就化学转化率而言是理想的,但它还隐含着较高的毒性潜力。此类交联剂的加工需要特殊的保护措施以满足有关的安全条款和职业卫生学的要求。另外,以这种方式改性的聚合物的使用似乎也成问题。
多官能醇也已知可用作交联剂。例如EP-A-0372981,US-4666983或US-5385983教导了亲水性多元醇的使用或多羟基表面活性剂的使用。根据这些文件,反应是在120-250℃的温度下进行的。该方法的缺点是导致交联的酯化反应甚至在此温度下仍然比较缓慢。
因此,目的是,通过使用相对缓慢反应但仍然可与羧基反应的化合物,以尽可能短的反应时间和尽可能低的温度实现与现有技术中的情况一样好或更好的凝胶相或表面后交联。理想地,主反应条件应该与使用高反应活性环氧化物时的那些相同。
现已令人惊奇地发现,这一目的能够通过使用双-和多-2-噁唑烷酮而以突出的效果得以实现。尤其,这些交联剂的反应活性能够通过添加有机或无机酸性催化剂而提高。适宜的催化剂是已知的无机酸,它们与碱金属或与铵的酸盐,以及它们的酸酐。适宜的有机催化剂是已知的羧酸,磺酸和氨基酸。
本发明提供吸水性聚合物的表面后交联的方法,其中聚合物用表面后交联溶液处理且在处理过程中或处理之后通过升温进行后交联并被干燥,其中交联剂包括溶于惰性溶剂中的、包含以下通式的结构单元的双-2-噁唑烷酮或多-2-噁唑烷酮,或双-2-噁唑烷酮和多-2-噁唑烷酮的混合物,其中R1是支化或未支化C1-C18-亚烷基,支化或未支化C2-C18-亚链烯基,C5-C8-亚环烷基,亚苯基,亚萘基,亚蒽基,烃取代的亚苯基、亚萘基或亚蒽基或另外的取代或未被取代的C6-C18-亚芳基,R2是支化或未支化C1-C18-亚烷基和n是1-50的整数。
其中R1是亚烷基或亚链烯基,它优选是具有3-12个、尤其5-10个碳原子的链长度的基团。R2优选是具有3-12个、尤其5-10个碳原子的链长度的亚烷基。
通式1的末端结构单元是端基封闭的。所使用的端基是能够引入到双-2-噁唑烷酮或多-2-噁唑烷酮中并在这些化合物上是化学稳定的任何基团。用于将通式1的结构单元封端的适宜基团的例子可以是氢,支化或未支化C1-C18-烷基,支化或未支化C2-C18-链烯基,苯基,萘基,蒽基,烃取代的苯基、萘基或蒽基或另外的取代或未被取代的C6-C18芳基。
多-2-噁唑烷酮优选包括n个双2-噁唑烷酮单元。
n优选是在1-10之间、特别优选在3-6之间的数。后交联温度优选是在50-250℃之间,尤其50-200℃和特别100-180℃之间。
为了加速表面后交联反应,酸性催化剂可加入到反应混合物中。在本发明的方法中使用的催化剂是所有的无机酸,它们的相应酸酐,和/或有机酸和它们的相应酸酐。实例是硼酸,硫酸,氢碘酸,磷酸,酒石酸,乙酸和甲苯磺酸。也适宜的尤其是它们的聚合物形式,酸酐,以及对于多元酸的情况是酸盐形式。其实例是氧化硼,三氧化硫,五氧化二磷,和磷酸二氢铵。
本发明的方法优选是通过将表面后交联剂的溶液喷射到干燥基础聚合物粉末上来进行的。在喷雾施用之后,聚合物粉末被加热干燥,有可能在干燥之前或过程中发生交联反应。在反应混合器和喷射混合器或混合和干燥***如Ldige混合器,BEPEX混合器,NAUTA混合器,SHUGGI混合器或PROCESSALL装置中交联剂溶液的喷雾施用是优选的。而且,还有可能使用流化床干燥器。通过加热外壳体或通过吹入热空气,干燥可在混合器本身中进行。同样适宜的是下游干燥器如盘架干燥机、旋转干燥器或可加热的螺杆。做为选择的措施,例如共沸蒸馏可用作干燥技术。在反应混合器或干燥器中在优选温度下的优选停留时间是5-90分钟,优选低于30分钟和非常优选低于10分钟。
作为惰性溶剂,优选水及水与单官能醇或多官能醇的混合物。然而,有可能使用所有可与水无限混溶的有机溶剂,例子是某些酯和酮,它们在工艺条件下本身是不反应的。当使用醇/水混合物时,该溶液的醇含量例如是10-90wt%,优选30-70wt%,和尤其40-60wt%。能够使用可与水无限混溶的任何醇,并且可以是两种或多种醇的混合物(例如甲醇+甘油+水)。特别优选的是在水溶液中使用下述醇类:甲醇,乙醇,异丙醇,乙二醇和特别优选1,2-丙二醇和1,3-丙二醇。表面后交联溶液使用比例是基于聚合物质量的1-20wt%。特别优选使用相当于聚合物重量的2.5-15wt%的溶液。交联剂本身以基于所使用聚合物的0.01-1.0wt%的量使用。
吸水性聚合物优选是聚合丙烯酸或聚丙烯酸盐。这一吸水性聚合物的制备是通过文献中已知的方法制备的。优选的是包括交联共聚单体(0.001-10mol%)的聚合物,但非常优选的是通过使用多官能烯属不饱和的、可另外携带至少一个羟基的一种自由基交联剂(如季戊四醇三烯丙基醚或三羟甲基丙烷二烯丙基醚)由自由基加聚反应获得的聚合物。
用于本发明方法中的亲水性可高度溶胀的水凝胶尤其是由(共)聚合的亲水性单体组成的聚合物,一种或多种亲水性单体在合适接枝基质物上的接枝(共)聚合物,交联纤维素醚或交联淀粉醚,或可在含水液体中溶胀的天然产物例如瓜耳树胶衍生物。这些水凝胶对于现有技术领域中的普通人员来说是已知并描述在例如US-4286082,DE-C-2706135,US-4340706,DE-C-3713601,DE-C-2840010,DE-A-4344548,DE-A-4020780,DE-A-4015085,DE-A-3917846,DE-A-3807289,DE-A-3533337,DE-A-3503458,DE-A-4244548,DE-A-4219607,DE-A-4021847,DE-A-3831261,DE-A-3511086,DE-A-3118172,DE-A-3028043,DE-A-4418881,EP-A-0801483,EP-A-0455985,EP-A-0467073,EP-A-0312952,EP-A-0205874,EP-A-0499774,DE-A-2612846,DE-A-4020780,EP-A-0205674,US-5145906,EP-A-0530438,EP-A-0670073,US-4057521,US-4062817,US-4525527,US-4295987,US-5011892,US-4076663或US-4931497中。上述专利文献的内容十分清楚地被引入本文供参考。
适合于制备这些亲水性可高度溶胀的水凝胶的亲水性单体的例子是可聚合的酸类,如丙烯酸,甲基丙烯酸,乙烯基磺酸,乙烯基膦酸,马来酸及其酸酐,富马酸,衣康酸,2-丙烯酰胺基-2-甲基丙烷磺酸,2-丙烯酰胺基-2-甲基丙烷膦酸,以及在每种情况下它们的盐例如钠、钾或铵盐,它们的酰胺,羟烷基酯,以及氨基-或铵-官能化酯和酰胺。其它也合适的是水溶性的N-乙烯基酰胺或二烯丙基二甲基氯化铵。优选的亲水性单体是以下通式2的化合物其中
R3是氢,甲基或乙基,
R5是氢,甲基,乙基或羧基,
R6是氢,氨基-(C1-C4)-烷基,羟基-(C1-C4)-烷基,碱金属离子或铵离子,和
R7是磺酰基,膦酰基或羧基,或这些基团的碱金属或铵盐。
(C1-C4)-链烷醇的例子是甲醇,乙醇,正丙醇和正丁醇。特别优选的亲水性单体是丙烯酸和甲基丙烯酸及其碱金属盐或铵盐,例如丙烯酸钠、丙烯酸钾和丙烯酸铵。
可通过烯属不饱和酸或它们的碱金属盐或铵盐的接枝共聚反应获得的、亲水性水凝胶的适宜接枝基质物在来源上可以是天然的或人工合成。实例是淀粉、纤维素和纤维素衍生物,以及其它多糖和低聚糖,聚亚烷基氧化物,特别是聚环氧乙烷和聚环氧丙烷,和亲水性聚酯。
R8和R9相互独立地是氢、烷基、链烯基或酰基,
X是氢或甲基,和
n是1到10,000的整数。
R8和R9优选是氢,(C1-C4)-烷基,(C2-C6)-链烯基或苯基。特别优选的水凝胶是描述在US-A-4931497,US-A-5011892和US-A-5041496中的聚丙烯酸盐、聚甲基丙烯酸盐和接枝共聚物。
亲水性可高度溶胀的水凝胶优选是交联形式;即,它们包括具有至少两个已被共聚合到聚合物网络中而引入的双键的化合物。特别适宜的交联剂是N,N’-亚甲基双丙烯酰胺和N,N’-亚甲基双甲基丙烯酰胺,不饱和一元或多元羧酸与多元醇的酯(如二丙烯酸酯或三丙烯酸酯),例子是丁二醇和乙二醇的二丙烯酸酯和二甲基丙烯酸酯和三羟甲基丙烷三丙烯酸酯,以及烯丙基化合物如(甲基)丙烯酸烯丙基酯,氰尿酸三烯丙基酯,马来酸二烯丙酯,聚烯丙基酯,四烯丙氧基乙烷,三烯丙基胺,四烯丙基乙二胺,磷酸的烯丙基酯,描述在例如EP-A-0343427中的乙烯基膦酸衍生物。然而,在本发明方法中,特别优选使用聚烯丙基醚作为交联剂和通过丙烯酸的酸性均聚反应制得的水凝胶。适宜的交联剂是季戊四醇三-和四烯丙基醚,聚乙二醇二烯丙基醚,单乙二醇二烯丙基醚,甘油二-和三烯丙基醚,基于山梨糖醇的聚烯丙基醚,及其烷氧基化物变体。
亲水性可高度溶胀的水凝胶可通过常规的聚合方法制备。优选的是通过已知为凝胶聚合的一种方法在水溶液中的加聚反应。在这一方法中,例如,将一种或多种亲水性单体和如果需要的话合适接枝基质物的15-50wt%浓度水溶液是在自由基引发剂存在下,优选没有机械混合,利用Trommsdorff-Norrish效应(Makromol.Chem.1947)169)进行聚合。
聚合反应可以在0℃和150℃之间,优选在10℃和100℃之间的温度范围内,在大气压力或在提高或降低的压力下进行。一般情况,聚合也可在惰性气氛下,优选在氮气之下进行。
聚合反应可使用高能电磁辐射或通过常规的化学聚合引发剂来引发。后者的例子是有机过氧化物,如过氧化苯甲酰,叔丁基过氧化氢,过氧化丁酮和氢过氧化枯烯,偶氮化合物,如偶氮二异丁腈,和无机过氧化合物,如(NH4)2S2O8,K2S2O8,或H2O2。如果需要,这些物质可与还原剂如连二亚硫酸钠或硫酸亚铁(II)结合使用,或与氧化还原体系结合使用。氧化还原体系包括还原性组分,它通常是脂族或芳族亚磺酸,如苯亚磺酸或甲苯亚磺酸或这些酸类的衍生物,如DE-C-1301566中所述的亚磺酸、醛或氨基化合物的曼尼期(Mannich)加合物。
聚合物的质量能够通过进一步继续在50-130℃、优选70-100℃的温度范围内对聚合物凝胶加热几个小时而得到改进。
有可能使用常规的中和剂,优选碱金属氢氧化物或碱金属氧化物,和特别优选氢氧化钠、碳酸钠或碳酸氢钠,将所获得的凝胶中和到例如0-100mol%的程度(基于所使用的单体),优选25-100mol%和特别优选50-85mol%。中和通常是在中和剂中以水溶液形式或优选以固体形式混合来进行。为此目的,凝胶利用例如破碎机进行机械粉碎,将中和剂喷射、撒布或倾倒在其上面,然后小心地混合。为了均化,所获得的凝胶物料再数次经过破碎机。
中和的凝胶物料然后用带式干燥器或辊式干燥器进行干燥,直至残留水分含量低于10wt%、优选低于5wt%为止。干燥后的水凝胶然后进行研磨和过筛,通常选择的研磨装置是辊式破碎机,针磨或振动球磨机。过筛后的水凝胶的优选粒度是在45-1000μm,特别优选45-850μm和非常优选200-850μm范围内。
根据本发明,含丙烯酸酯的聚合物可使用双或多2-噁唑烷酮交联。本发明的新型交联剂可通过异氰酸酯和双环氧化合物(双2-噁唑烷酮)或二异氰酸酯和双环氧化合物(多2-噁唑烷酮)反应来制备。
R1和R2如以上所定义。在多2-噁唑烷酮的制备中,有可能将一定量的单异氰酸酯加入到反应混合物中。当它们被引入后可终止加聚反应。单异氰酸酯的添加量在这种情况下必须使得达到所需要的聚2-噁唑烷酮的链长度。携带异氰酸酯基的基团则变成了端基。在聚合物的重复单元中因加聚反应形成了两个噁唑烷酮单元,其中n是大于1的整数。加聚反应在极性非质子传递溶剂(它在现场温度下既不与二异氰酸酯反应也不与双环氧化物反应)中优先发生但不是唯一的。脂肪族二异氰酸酯与双环氧化合物产生可溶于例如二甲基甲酰胺中的低熔点灰白色产物,而芳族二异氰酸酯的反应一般得到高熔点的深色和不易溶解的产物。
当使用芳族二异氰酸酯时产物常常具有差的溶解度和高熔点,所以优选的是脂肪族二异氰酸酯与脂族或芳族双环氧化合物一起使用。
本发明还提供由上述方法制备的产物。
本发明另外提供由本发明的方法所制得的产物在卫生制品、包装材料和无纺织物中的用途。
为了确定表面后交联的质量,干燥的水凝胶然后使用下面所述的现有技术的试验方法进行测试:
方法:
1)离心保留容量(CRC):
该方法测量水凝胶在茶叶袋中的自由溶胀性。大约0.200g干燥水凝胶被放入到密封的茶叶袋(规格:60mm×60mm,Dexter 1234T纸)中并在0.9wt%浓度氯化钠溶液中浸泡30分钟。茶叶袋然后在商购旋转干燥器(Bauknecht WS 130,1400rpm,篮子直径230mm)中旋转3分钟。液体吸收的体积是通过将离心的茶叶袋称重来测定的。茶叶袋本身(没有水凝胶的茶叶袋)的吸收容量通过测定空白值来折算,这一空白值从称重结果(有溶胀水凝胶的茶叶袋)中扣除。
保留率CRC[g/g]=(有水凝胶的茶叶袋称重结果-空白值-水凝胶的最初重量)/水凝胶的最初重量
2)载荷下的吸收能力(0.3/0.5/0.7psi):
对于载荷下的吸收能力,0.900g干燥水凝胶均匀分布在测量池(measuring cell)的筛状底部(screen base)上。测量池由有机玻璃圆筒(高度=50mm,直径=60mm)组成,它的筛状底部是通过在将圆筒底部粘接在钢丝网筛(筛孔尺寸36微米,或400目)上形成的。在均匀分布的水凝胶上放置盖板并承载适当的重量。测量池然后放置在处在多孔玻璃滤板上的滤纸(S&S 589黑带,直径=90mm)上,而滤板本身处在含有一定量的0.9wt%浓度氯化钠溶液的培养皿(高度30mm,直径=200mm)中,溶液量应使得在实验的开始液面与玻璃过滤料(frit)的顶端齐平。然后让水凝胶吸收该盐溶液达60分钟。
随后,从滤板上取下有溶胀凝胶的完整测量池,在取出载荷之后对装置重新称重。
载荷下的吸收能力(AUL)计算如下:
AUL[g/g]=(Wb-Wa)/Ws其中Wb是装置+溶胀后的凝胶两者的质量,Wa是装置的质量+溶胀前凝胶的最初重量,和Ws是干燥水凝胶的初始重量。
该装置是测量圆筒和盖板组成。
实施例:
根据本发明的实施例揭示了表面后交联对超吸收性聚合物的影响。正如本技术领域中普通技术人员所知道的,后交联可通过测量离心保留量(CRC)和载荷下的吸收能力(AUL)来确定效果。对于表面交联,CRC典型地是在5-10g/g之间,而在0.7psi下的AUL提高了大约10和在0.3psi下的AUL提高了20g/g以上。
实施例1:基础聚合物
在40升的塑料桶中,6.9千克的纯丙烯酸用23千克水稀释。在搅拌下向该溶液中添加45g的季戊四醇三烯丙基醚,密封的桶在通入氮气之后保持惰性。通过添加大约400mg过氧化氢和200mg抗坏血酸引发聚合反应。在反应结束后,凝胶进行机械粉碎,然后以足以达到75mol%的中和度(基于所使用的丙烯酸)的量添加氢氧化钠溶液。中和的凝胶然后在辊式干燥器上干燥,用针磨进行研磨,最后过筛分离。这是在后面的实施例中使用的基础聚合物。
实施例1a和1b
基础聚合物在韦林氏(Waring)实验室混合器中用具有下述组成的交联剂溶液喷射:5%甲醇,5%水,0.20%来自制备实施例1的双噁唑烷酮,它们全部基于所使用的聚合物,随后,在对流干燥箱中将一部分湿产物在170℃下处理60分钟和剩余部分在170℃处理90分钟。干燥的产物通过在850微米下过筛进行分离,以除去块状物。这一实施例揭示了当使用双噁唑烷酮时,为实现表面后交联可以不需要任何二醇组分。
实施例2a和2b
按实施例1中制备的基础聚合物在韦林氏(Waring)实验室混合器中用交联剂溶液喷射。在这种情况下,该溶液具有可以达到以下剂量的组成(基于所使用的基础聚合物):0.20wt%来自制备实施例2的双噁唑烷酮,5wt%丙二醇和5wt%水。湿聚合物然后在175℃分别干燥30分钟和60分钟。
实施例3a和3b
按实施例1中制备的基础聚合物在韦林氏(Waring)实验室混合器中用交联剂溶液喷射。在这种情况下,该溶液具有可以达到以下剂量的组成(基于所使用的基础聚合物):0.20wt%来自制备实施例3的多-2-噁唑烷酮,5wt%丙二醇,5wt%水和0.2wt%硼酸。湿聚合物然后在175℃分别干燥60分钟和90分钟。
实施例4a和4b
按实施例1中制备的基础聚合物在韦林氏(Waring)实验室混合器中用交联剂溶液喷射。在这种情况下,该溶液具有可以达到以下剂量的组成(基于所使用的基础聚合物):0.20wt%来自制备实施例4的多-2-噁唑烷酮,5wt%丙二醇,5wt%水和0.2wt%磷酸二氢铵。温聚合物然后在175℃分别干燥60分钟和90分钟。
实施例5a和5b
按实施例1中制备的基础聚合物在韦林氏(Waring)实验室混合器中用交联剂溶液喷射。在这种情况下,该溶液具有可以达到以下剂量的组成(基于所使用的基础聚合物):0.20wt%来自制备实施例5的多-2-噁唑烷酮,5wt%丙二醇,5wt%水和0.2wt%磷酸二氢铵。湿聚合物然后在175℃分别干燥60分钟和90分钟。
实施例6a和6b
按实施例1中制备的基础聚合物在韦林氏(Waring)实验室混合器中用交联剂溶液喷射。在这种情况下,该溶液具有可以达到以下剂量的组成(基于所使用的基础聚合物):0.20wt%来自制备实施例2的双噁唑烷酮,5wt%甲醇,5wt%水和0.2wt%磷酸二氢铵。这一实施例揭示了当使用双噁唑烷酮时,为实现表面后交联可以不需要任何二醇组分。湿聚合物然后在175℃分别干燥60分钟和90分钟。
实施例7a和7b
按实施例1中制备的基础聚合物在韦林氏(Waring)实验室混合器中用交联剂溶液喷射。在这种情况下,该溶液具有可以达到以下剂量的组成(基于所使用的基础聚合物):0.20wt%来自制备实施例5的多-2-噁唑烷酮,5wt%甲醇,5wt%水和0.2wt%磷酸二氢铵。这一实施例揭示了当使用多-2-噁唑烷酮时,为实现表面后交联可以不需要任何二醇组分。湿聚合物然后在175℃分别干燥60分钟和90分钟。
双-2-噁唑烷酮的制备,制备实施例1
间苯二酚二缩水甘油基醚和异氰酸苯酯的反应产物
在装有搅拌器、回流冷凝器和进气管的三颈烧瓶中在氮保护气氛中将0.1mol的间苯二酚二缩水甘油基醚(ABCR)通过滴加与0.2mol异氰酸苯基酯(Aldrich)混合,混合物被加热至DMF(Aldrich)的沸点。反应溶液随后在回流下搅拌3-4小时,然后冷却。产物用甲醇沉淀和从DMF/甲醇中重结晶。
以高产率获得了熔点为202℃的褐黄色化合物。IR谱显示了噁唑烷酮在1750cm-1处的典型谱带。元素分析的结果是:C:67.2%,H:5.3%,N:6.0%。
双-2-噁唑烷酮的制备,制备实施例2
双酚A二缩水甘油醚和异氰酸苯基酯的反应产物
在装有搅拌器、回流冷凝器和进气管的三颈烧瓶中在氮保护气氛中将0.1mol的双酚A二缩水甘油基醚(Aldrich)通过滴加与0.2mol异氰酸苯基酯混合,混合物被加热至DMF(Aldrich)的沸点。反应溶液随后在回流下搅拌3-4小时,然后冷却。产物用甲醇沉淀和从水/甲醇(3∶1)中重结晶。以高产率获得了熔点为131℃的褐黄色化合物。IR谱显示了噁唑烷酮在1760cm-1处的典型谱带。元素分析的结果是:C:72.2%,H:5.4%,N:5.0%。
多-2-噁唑烷酮的制备,制备实施例3
在装有搅拌器、回流冷凝器和进气管的三颈烧瓶中在氮保护气氛中将0.1mol的双酚A二缩水甘油基醚通过滴加与0.1mol六亚甲基二异氰酸酯混合,混合物被加热至DMF的沸点。反应溶液随后在回流下搅拌3-4小时,然后冷却。产物用水沉淀,溶解在DMF中和再用水沉淀。产物溶于甲醇和甲醇/水混合物中。它是熔化范围在105和120℃之间和在蒸馏水中Staudinger指数ηsp/C为0.024l/g的白色固体。
多-2-噁唑烷酮的制备,制备实施例4
在装有搅拌器、回流冷凝器和进气管的三颈烧瓶中在氮保护气氛中将0.1mol的丁二醇二缩水甘油基醚(=1,4-双(2,3-环氧基丙氧基)丁烷)通过滴加与0.1mol六亚甲基二异氰酸酯混合,混合物被加热至DMF的沸点。反应溶液随后在回流下搅拌3-4小时,然后冷却。产物用甲醇沉淀和从水/甲醇(3∶1)中重结晶。得到了可与甲醇和甲醇/水混溶的浅黄色油状液体。
多-2-噁唑烷酮的制备,制备实施例5
在装有搅拌器、回流冷凝器和进气管的三颈烧瓶中在氮保护气氛中将0.1mol的已二醇二缩水甘油基醚(=1,4-双(2,3-环氧基丙氧基)己烷(ABCR))通过滴加与0.1mol六亚甲基二异氰酸酯混合,混合物被加热至DMF的沸点。反应溶液随后在回流下搅拌3-4小时,然后冷却。产物用甲醇沉淀和从水/甲醇(3∶1)中重结晶。得到了可与甲醇和甲醇/水混溶的浅黄色油状液体。
这里,干燥温度和干燥时间涉及到已用表面-后交联溶液喷射的基础聚合物的热处理。
Claims (10)
2.根据权利要求1所要求的方法,其中吸水性聚合物是聚合丙烯酸或聚丙烯酸盐,尤其通过使用多官能烯属不饱和的、可另外携带一个或多个游离羟基的自由基交联剂由自由基加聚反应获得的聚合丙烯酸或聚丙烯酸盐。
3.根据权利要求1或2中所要求的方法,其中用于交联的催化剂包括无机酸,它们的酸酐,或有机酸或它们的酸酐。
4.根据权利要求3中所要求的方法,其中酸是硼酸,硫酸,氢碘酸,磷酸,酒石酸,乙酸或甲苯磺酸或它们的聚合形式、酸酐或酸盐当中的一种。
5.根据权利要求1-4中一项或多项所要求的方法,其中惰性溶剂是水,水与可无限溶于水中的有机溶剂的混合物,或水与单官能醇或多官能醇的混合物。
6.根据权利要求5所要求的方法,其中如果使用醇/水混合物,则该溶液的醇含量是10-90wt%,优选30-70wt%。
7.根据权利要求5或6所要求的方法,其中醇是甲醇,乙醇,异丙醇,乙二醇,1,2-丙二醇或1,3-丙二醇。
8.根据权利要求1-4中一项或多项所要求的方法,其中表面后交联溶液的用量是基于聚合物质量的1-20wt%,尤其2.5-15wt%。
9.由根据权利要求1-8中一项或多项所要求的方法制得的吸液性聚合物。
10.由根据权利要求1-8中一项或多项所要求的方法制得的聚合物在卫生制品、包装材料或无纺织物中的应用。
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1999
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- 1999-02-24 CA CA002319453A patent/CA2319453A1/en not_active Abandoned
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US6503979B1 (en) | 2003-01-07 |
CA2319453A1 (en) | 1999-09-02 |
EP1058695A1 (de) | 2000-12-13 |
BR9908248A (pt) | 2000-10-31 |
DE19807992C1 (de) | 1999-07-15 |
JP2002504597A (ja) | 2002-02-12 |
KR20010041357A (ko) | 2001-05-15 |
AU2726199A (en) | 1999-09-15 |
ID25455A (id) | 2000-10-05 |
BR9908248B1 (pt) | 2009-01-13 |
DE59906513D1 (de) | 2003-09-11 |
EP1058695B1 (de) | 2003-08-06 |
JP4210433B2 (ja) | 2009-01-21 |
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